It is known that ethylene copolymers having pendant carboxylic acid groups are reactive with metal oxides, metal hydroxides, and metal hydrates to form metal salts of at least some of the carboxylic acid groups. The carboxylic acid groups are usually those provided by acrylic acid or methacrylic acid, or other such olefin acids, when copolymerized or interpolymerized with ethylene.
The ethylene/carboxyl-containing copolymers preferred in the present invention are commercially available, especially those of the type known as "interpolymer", but may also be of the type known as "graft copolymers" and "block copolymers". These expressions are known to practitioners of the art. Interpolymers are made by polymerizing a mixture of the monomers; graft copolymers are made by grafting olefin acid groups onto a polyethylene chain; block copolymers are those wherein long polymer chains comprise chain segments of a polymerized plurality of ethylene units and segments of a polymerized plurality of the carboxyl-containing monomer units.
As used herein the expression "olefin acids" refers to olefinically-unsaturated carboxylic acids which are copolymerizable with ethylene, especially acrylic acid, methacrylic acid, crotonic acid, and 1-buteneoic acid, most especially acrylic acid and methacrylic acid.
Patents which disclose interpolymerizations of ethylene and unsaturated carboxylic acids in a steady state reaction at high temperature and high pressure in a stirred reactor in the presence of a free-radical initiator are, e.g., Canadian Patent No. 655,298 (and its U.S. counterpart U.S. Pat. No. 4,351,931); U.S. Pat. No. 3,239,270; U.S. Pat. No. 3,520,861; U.S. Pat. No. 3,658,741; U.S. Pat. No. 3,884,857; U.S. Pat. No. 3,988,509; U.S. Pat. No. 4,248,990; and U.S. Pat. No. 4,252,924.
Also included as a part of the present invention are polyethylenes and, preferably, certain ethylene interpolymers of the linear low density variety, known by the acronym LLDPE. These LLDPE resins are distinguishable from the non-linear (branched) low density polyethylene (LDPE) made by homopolymerizing ethylene using free-radical initiators; the LDPE resins contain branched chains of polymerized monomer units pendant from the main polymer "backbone" and generally have densities in the range of about 0.910 to about 0.935 gms/cc.
The LLDPE resins are also distinguishable from the linear high density polyethylene (HDPE) resins by the fact that these LLDPE resins are prepared by interpolymerizing ethylene with enough of a higher alpha-olefin to yield a linear ethylene copolymer which has a density, generally, in the same range of the LDPE. Linear HDPE generally has a density in the range of about 0.941 to about 0.965 gms/cc. Both HDPE and LLDPE are linear polymers, prepared using a coordination catalyst, e.g., the well-known Ziegler catalyst, or modifications thereof such as the Natta catalyst.
As used in this disclosure, the expression "ethylene polymers" refers to the homopolymers (LDPE and HDPE) and the ethylene/olefn interpolymers (LLDPE).
Some teachings about the differences in LDPE, HDPE, and LLDPE resins are found, e.g., in U.S. Pat. No. 4,327,009. A method of making various LLDPE resins is disclosed, e.g., in U.S. Pat. No. 4,076,698.
The addition of metal oxides to molten carboxyl-containing ethylene polymers, e.g., ethylene/acrylic acid (EAA) or ethylene/methacrylic acid (EMAA) is usually done by carrying the metal compounds, as a hydroxide or hydrate, in an aqueous carrier, employing, in some cases, an acid aqueous carrier to solubilize the metal. This causes bubbling of the water (as steam) and often has deleterious effects on the product sought to be made. See, e.g., U.S. Pat. No. 4,440,893 which proposes the use of an acetylene peroxy compound to alleviate bubble formation.
Directly blending dry anhydrous metal oxides (e.g. MgO, CaO, BaO, ZnO) into molten EAA or EMAA can be performed to avoid the use of aqueous carriers for the metal oxide, but because of the reactivity of the carboxylic acid groups with the metal oxides, nonhomogeneous blending often occurs.
U.S. Pat. No. 4,420,580 discloses that inorganic metal fillers, e.g. polyvalent metal oxides, are made more compatible with a polyolefin resin, e.g., linear low density ethylene copolymers, by incorporating an ethylene/acrylic acid copolymer into a molten mixture of the polyolefin/metal oxide. In these blends, the polyolefin is present in significantly greater concentration than is the ethylene/acrylic acid copolymer.
Patents pertaining to ionomers are, e.g., U.S. Pat. No. 3,249,570; U.S. Pat. No. 3,264,272; U.S. Pat. No. 3,322,734; U.S. Pat. No. 3,379,702; U.S. Pat. No. 3,404,134; U.S. Pat. No. 3,649,578; U.S. Pat. No. 3,789,035; U.S. Pat. No. 3,969,434; and U.S. Pat. No. 3,970,626.
It is an object of the present invention to provide a means for blending metal oxides into molten ethylene copolymers having pendant carboxylic acid groups which avoids the use of aqueous carriers.
Another object is that of blending dry metal oxides into molten ethylene copolymers having pendant carboxylic acid groups, whereby excessive reaction of the metal oxide with the said acid groups is substantially minimized, thereby permitting a more uniform dispersion of the metal oxide to be made.
Yet another object is that of preparing a curable or cross-linkable composite comprising an ethylene copolymer, having pendant carboxylic acid groups, and having substantially uniformly dispersed therein at least one metal oxide.
These objects are substantially attained by the ways and means disclosed herein.